organic compounds
1,3-Dimethoxy-2-methylimidazolium bis(trifluoromethanesulfonyl)imide
aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80, 6020 Innsbruck, Austria
*Correspondence e-mail: gerhard.laus@uibk.ac.at
The title molecular salt, C6H11N2O2+·C2F6NO4S2−, was obtained by the methylation of 1-hydroxy-2-methylimidazole 3-oxide and subsequent ion metathesis. In the crystal, C—H⋯O=S hydrogen bonds and O⋯π interactions are observed.
Keywords: crystal structure; anion O⋯π interactions; imidazole; bis(triflimide).
CCDC reference: 1481051
Structure description
The molecular structure of the title compound is shown in Fig. 1. The ions which build this salt, both 1,3-dialkyloxyimidazolium cations (Laus et al., 2010) and the bis(triflimide) anion (Bentivoglio et al., 2009; Laus et al., 2011), are known to exist as syn/anti conformers in the solid state. Thus, the methoxy substituents of the cation adopt an anti conformation with a C5—O1⋯O2—C6 torsion angle of 170.6 (4)°. The bis(triflimide) anion also assumes an anti conformation with a C7—S1⋯S2—C8 torsion angle of 174.9 (2)°. Each cation donates three C—H⋯O=S hydrogen bonds to three anions (Fig. 2). The hydrogen-bond parameters are summarized in Table 1. An intriguing intermolecular interaction between atom O3 of the anion and the π system of the imidazolium ring is observed. The pertinent O3⋯Cg distance is 2.971 Å, where Cg is the centroid of the heterocyclic ring. This interaction is directional with an S1=O3⋯Cg angle of 152°. The crystal packing is shown in Fig. 3.
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The cation in the structure of the related 1,3-dimethoxy-2-methylimidazolium tris(pentafluoroethyl)trifluorophosphate displayed a syn geometry (Laus et al., 2007). Anion⋯π interactions have been observed in related imidazolium salts (Froschauer et al., 2012).
Synthesis and crystallization
A suspension of 1-hydroxy-2-methylimidazole-3-oxide (5.09 g, 44.6 mmol) and dimethyl sulfate (9.0 ml, 100 mmol) in H2O (5.0 ml) was stirred at room temperature for 30 min. Calcium carbonate (6.35 g, 63.4 mmol) and H2O (6.0 ml) were then added to the slurry, and a slight increase of temperature was observed. The mixture was stirred for 15 h. Then hydrochloric acid (36%; 11.0 ml, 129.2 mmol) was added in portions and stirred for 2 h, resulting in a clear solution. Lithium bis(trifluoromethanesulfonyl)imide (13.0 g, 44.9 mmol) was added, whereupon crystallization of the product occurred. After stirring for 1 h, the mixture was extracted with CH2Cl2 (3 × 50 ml). The combined organic phases were then washed with H2O (100 ml) and dried over Na2SO4. The solvent was removed under reduced pressure, and the product was dried at 75°C in vacuum (< 1 mbar). On cooling to room temperature the product was obtained as a colourless crystalline solid (yield 97%), mp. 66°C.
1H NMR (300 MHz, CD2Cl2): δ 2.73 (s, 3H), 4.26 (s, 6H), 7.53 (s, 2H) p.p.m. 13C NMR (75 MHz, CD2Cl2): δ 8.0, 69.7, 116.3, 120.4 (q, J = 321.1 Hz), 139.1 p.p.m. IR: ν 3142, 1594, 1459, 1333, 1183, 1136, 1111, 1048, 958, 938, 791, 762, 740, 728, 713, 647, 611, 567, 512, 407 cm−1.
Refinement
Crystal data, data collection and structure . The crystal studied was found to be a racemic twin.
details are summarized in Table 2Structural data
CCDC reference: 1481051
10.1107/S2414314616008245/hb4048sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616008245/hb4048Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616008245/hb4048Isup3.mol
Supporting information file. DOI: 10.1107/S2414314616008245/hb4048Isup4.cml
A suspension of 1-hydroxy-2-methylimidazole-3-oxide (5.09 g, 44.6 mmol) and dimethyl sulfate (9.0 ml, 100 mmol) in H2O (5.0 ml) was stirred at room temperature for 30 min. Calcium carbonate (6.35 g, 63.4 mmol) and H2O (6.0 ml) were then added to the slurry, and a slight increase of temperature was observed. The mixture was stirred for 15 h. Then hydrochloric acid (36%; 11.0 ml, 129.2 mmol) was added in portions and stirred for 2 h, resulting in a clear solution. Lithium bis(trifluoromethanesulfonyl)imide (13.0 g, 44.9 mmol) was added, whereupon crystallization of the product occurred. After stirring for 1 h, the mixture was extracted with CH2Cl2 (3× 50 ml). The combined organic phases were then washed with H2O (100 ml) and dried over Na2SO4. The solvent was removed under reduced pressure, and the product was dried at 75°C in vacuum (< 1 mbar). On cooling to room temperature the product was obtained as a colourless crystalline solid (yield 97%), mp. 66°C.
1H NMR (300 MHz, CD2Cl2): δ 2.73 (s, 3H), 4.26 (s, 6H), 7.53 (s, 2H) p.p.m. 13C NMR (75 MHz, CD2Cl2): δ 8.0, 69.7, 116.3, 120.4 (q, J = 321.1 Hz), 139.1 p.p.m. IR: ν 3142, 1594, 1459, 1333, 1183, 1136, 1111, 1048, 958, 938, 791, 762, 740, 728, 713, 647, 611, 567, 512, 407 cm-1.
Crystal data, data collection and structure
details are summarized in Table 2. The crystal studied was found to be a racemic twin.The molecular structure of the title compound is shown in Fig. 1. The ions which build this salt, both 1,3-dialkyloxyimidazolium cations (Laus et al., 2010) and the bis(triflimide) anion (Bentivoglio et al., 2009; Laus et al., 2011), are known to exist as syn/anti conformers in the solid state. Thus, the methoxy substituents of the cation adopt an anti conformation with a C5—O1···O2—C6 torsion angle of 170.6 (4)°. The bis(triflimide) anion also assumes an anti conformation with a C7—S1···S2—C8 torsion angle of 174.9 (2)°. Each cation donates three C—H···O═S hydrogen bonds to three anions (Fig. 2). The hydrogen-bond parameters are summarized in Table 1. An intriguing intermolecular interaction between atom O3 of the anion and the π system of the imidazolium ring is observed. The pertinent O3···Cg distance is 2.971 Å, where Cg is the centroid of the heterocyclic ring. This interaction is directional with an S1═O3···Cg angle of 152°. The crystal packing is shown in Fig. 3.
The cation in the structure of the related 1,3-dimethoxy-2-methylimidazolium tris(pentafluoroethyl)trifluorophosphate displayed a syn geometry (Laus et al., 2007). Anion···π interactions have been observed in related imidazolium salts (Froschauer et al., 2012).
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2006).Fig. 1. The asymmetric unit of the title compound, showing the atom labels and 50% probability displacement ellipsoids for non-H atoms. | |
Fig. 2. The O3···π interaction and C—H···O═S hydrogen bonds are shown as dashed lines (see Table 1). The centroid of the imidazole ring is drawn as red sphere. | |
Fig. 3. The crystal packing of the title compound viewed along the b axis showing the O3···π interactions. |
C6H11N2O2+·C2F6NO4S2− | F(000) = 856 |
Mr = 423.32 | Dx = 1.648 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.4858 (6) Å | Cell parameters from 9895 reflections |
b = 14.0212 (6) Å | θ = 2.8–25.2° |
c = 9.8480 (4) Å | µ = 0.40 mm−1 |
β = 98.179 (1)° | T = 183 K |
V = 1706.51 (13) Å3 | Prism, colourless |
Z = 4 | 0.18 × 0.16 × 0.12 mm |
Bruker D8 QUEST PHOTON 100 diffractometer | 3088 independent reflections |
Radiation source: Incoatec Microfocus | 3020 reflections with I > 2σ(I) |
Multi layered optics monochromator | Rint = 0.027 |
Detector resolution: 10.4 pixels mm-1 | θmax = 25.3°, θmin = 2.2° |
φ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | k = −16→16 |
Tmin = 0.851, Tmax = 0.914 | l = −11→11 |
24313 measured reflections |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0576P)2 + 1.0708P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.033 | (Δ/σ)max < 0.001 |
wR(F2) = 0.092 | Δρmax = 0.35 e Å−3 |
S = 1.05 | Δρmin = −0.23 e Å−3 |
3088 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
228 parameters | Extinction coefficient: 0.0046 (10) |
2 restraints | Absolute structure: Flack x determined using 1476 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Hydrogen site location: inferred from neighbouring sites | Absolute structure parameter: 0.493 (15) |
C6H11N2O2+·C2F6NO4S2− | V = 1706.51 (13) Å3 |
Mr = 423.32 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 12.4858 (6) Å | µ = 0.40 mm−1 |
b = 14.0212 (6) Å | T = 183 K |
c = 9.8480 (4) Å | 0.18 × 0.16 × 0.12 mm |
β = 98.179 (1)° |
Bruker D8 QUEST PHOTON 100 diffractometer | 3088 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 3020 reflections with I > 2σ(I) |
Tmin = 0.851, Tmax = 0.914 | Rint = 0.027 |
24313 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.092 | Δρmax = 0.35 e Å−3 |
S = 1.05 | Δρmin = −0.23 e Å−3 |
3088 reflections | Absolute structure: Flack x determined using 1476 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
228 parameters | Absolute structure parameter: 0.493 (15) |
2 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.40336 (7) | 0.15962 (7) | 0.69953 (9) | 0.0461 (3) | |
S2 | 0.36096 (7) | 0.35188 (7) | 0.65521 (8) | 0.0441 (3) | |
O1 | 0.7855 (2) | 0.1723 (3) | 0.5887 (3) | 0.0505 (7) | |
O2 | 0.4893 (2) | 0.2163 (3) | 0.2448 (3) | 0.0572 (8) | |
O3 | 0.4986 (3) | 0.1675 (3) | 0.6408 (5) | 0.0886 (14) | |
O4 | 0.4032 (4) | 0.0997 (3) | 0.8175 (4) | 0.0898 (14) | |
O5 | 0.4036 (4) | 0.3477 (3) | 0.5317 (3) | 0.0791 (12) | |
O6 | 0.2665 (3) | 0.4073 (2) | 0.6611 (5) | 0.0843 (14) | |
N1 | 0.6963 (2) | 0.1528 (2) | 0.4931 (3) | 0.0372 (7) | |
N2 | 0.5662 (3) | 0.1719 (2) | 0.3361 (3) | 0.0402 (7) | |
N3 | 0.3443 (3) | 0.2542 (2) | 0.7295 (3) | 0.0412 (7) | |
C1 | 0.6403 (3) | 0.2208 (2) | 0.4199 (4) | 0.0325 (6) | |
C2 | 0.6576 (3) | 0.0640 (3) | 0.4565 (4) | 0.0471 (9) | |
H2 | 0.6848 | 0.0050 | 0.4944 | 0.057* | |
C3 | 0.5749 (4) | 0.0760 (3) | 0.3579 (5) | 0.0507 (10) | |
H3 | 0.5305 | 0.0276 | 0.3117 | 0.061* | |
C4 | 0.6552 (4) | 0.3241 (3) | 0.4334 (5) | 0.0528 (11) | |
H4A | 0.6018 | 0.3566 | 0.3665 | 0.079* | |
H4B | 0.7283 | 0.3410 | 0.4164 | 0.079* | |
H4C | 0.6455 | 0.3439 | 0.5263 | 0.079* | |
C5 | 0.7590 (4) | 0.1618 (4) | 0.7272 (4) | 0.0552 (11) | |
H5A | 0.8231 | 0.1759 | 0.7938 | 0.083* | |
H5B | 0.7007 | 0.2062 | 0.7406 | 0.083* | |
H5C | 0.7353 | 0.0963 | 0.7405 | 0.083* | |
C6 | 0.5176 (4) | 0.2109 (5) | 0.1079 (5) | 0.0747 (16) | |
H6A | 0.4620 | 0.2429 | 0.0436 | 0.112* | |
H6B | 0.5875 | 0.2422 | 0.1059 | 0.112* | |
H6C | 0.5227 | 0.1438 | 0.0814 | 0.112* | |
C7 | 0.3078 (4) | 0.1002 (4) | 0.5699 (6) | 0.0638 (13) | |
C8 | 0.4643 (4) | 0.4126 (4) | 0.7738 (5) | 0.0544 (11) | |
F1 | 0.3469 (4) | 0.0141 (3) | 0.5471 (5) | 0.1128 (14) | |
F2 | 0.2968 (4) | 0.1460 (3) | 0.4556 (4) | 0.1203 (18) | |
F3 | 0.2132 (3) | 0.0869 (3) | 0.6113 (5) | 0.1010 (13) | |
F4 | 0.4827 (3) | 0.4974 (3) | 0.7259 (4) | 0.0969 (12) | |
F5 | 0.5554 (3) | 0.3634 (3) | 0.7906 (4) | 0.0971 (13) | |
F6 | 0.4327 (3) | 0.4239 (3) | 0.8947 (3) | 0.0912 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0445 (5) | 0.0482 (5) | 0.0443 (5) | 0.0172 (4) | 0.0020 (4) | −0.0033 (4) |
S2 | 0.0394 (5) | 0.0472 (5) | 0.0427 (5) | −0.0042 (4) | −0.0043 (4) | 0.0151 (4) |
O1 | 0.0275 (11) | 0.090 (2) | 0.0318 (13) | −0.0063 (13) | −0.0019 (10) | −0.0038 (13) |
O2 | 0.0353 (14) | 0.094 (2) | 0.0408 (15) | 0.0187 (15) | −0.0008 (11) | 0.0098 (15) |
O3 | 0.0445 (18) | 0.108 (3) | 0.119 (3) | 0.0090 (18) | 0.029 (2) | −0.051 (3) |
O4 | 0.146 (4) | 0.058 (2) | 0.061 (2) | 0.042 (2) | −0.002 (2) | 0.0087 (17) |
O5 | 0.096 (3) | 0.104 (3) | 0.0363 (16) | −0.043 (2) | 0.0043 (17) | 0.0150 (17) |
O6 | 0.0490 (18) | 0.0506 (18) | 0.147 (4) | 0.0084 (15) | −0.009 (2) | 0.029 (2) |
N1 | 0.0255 (14) | 0.055 (2) | 0.0291 (15) | −0.0026 (13) | −0.0033 (11) | 0.0006 (12) |
N2 | 0.0335 (15) | 0.0503 (17) | 0.0360 (16) | 0.0028 (13) | 0.0020 (13) | 0.0020 (13) |
N3 | 0.0450 (16) | 0.0408 (16) | 0.0409 (15) | 0.0099 (13) | 0.0163 (13) | 0.0079 (13) |
C1 | 0.0285 (14) | 0.0385 (15) | 0.0316 (14) | −0.0005 (13) | 0.0079 (11) | 0.0022 (14) |
C2 | 0.055 (2) | 0.0349 (18) | 0.050 (2) | 0.0008 (16) | 0.0041 (17) | 0.0046 (16) |
C3 | 0.055 (2) | 0.046 (2) | 0.050 (2) | −0.0146 (18) | 0.0018 (18) | −0.0099 (17) |
C4 | 0.066 (3) | 0.041 (2) | 0.056 (2) | −0.0060 (18) | 0.024 (2) | −0.005 (2) |
C5 | 0.047 (2) | 0.086 (3) | 0.0307 (18) | −0.007 (2) | −0.0031 (16) | −0.0013 (18) |
C6 | 0.062 (3) | 0.126 (5) | 0.036 (2) | 0.030 (3) | 0.0037 (19) | 0.018 (3) |
C7 | 0.065 (3) | 0.062 (3) | 0.068 (3) | −0.010 (2) | 0.022 (2) | −0.019 (2) |
C8 | 0.051 (3) | 0.065 (3) | 0.046 (2) | −0.006 (2) | 0.0017 (19) | −0.0008 (19) |
F1 | 0.122 (3) | 0.084 (2) | 0.136 (3) | −0.003 (2) | 0.027 (3) | −0.062 (3) |
F2 | 0.148 (4) | 0.148 (4) | 0.0521 (19) | −0.063 (3) | −0.030 (2) | 0.006 (2) |
F3 | 0.070 (2) | 0.097 (3) | 0.141 (4) | −0.0255 (19) | 0.031 (2) | −0.030 (2) |
F4 | 0.108 (3) | 0.079 (2) | 0.100 (3) | −0.047 (2) | 0.002 (2) | 0.0081 (19) |
F5 | 0.0476 (17) | 0.131 (3) | 0.102 (3) | 0.0050 (18) | −0.0268 (16) | −0.040 (2) |
F6 | 0.122 (3) | 0.094 (2) | 0.0588 (17) | −0.018 (2) | 0.0192 (18) | −0.0246 (16) |
S1—O3 | 1.399 (4) | C2—H2 | 0.9500 |
S1—O4 | 1.434 (4) | C3—H3 | 0.9500 |
S1—N3 | 1.565 (3) | C4—H4A | 0.9800 |
S1—C7 | 1.820 (5) | C4—H4B | 0.9800 |
S2—O5 | 1.397 (4) | C4—H4C | 0.9800 |
S2—O6 | 1.421 (4) | C5—H5A | 0.9800 |
S2—N3 | 1.581 (3) | C5—H5B | 0.9800 |
S2—C8 | 1.823 (5) | C5—H5C | 0.9800 |
O1—N1 | 1.379 (4) | C6—H6A | 0.9800 |
O1—C5 | 1.456 (5) | C6—H6B | 0.9800 |
O2—N2 | 1.368 (4) | C6—H6C | 0.9800 |
O2—C6 | 1.444 (5) | C7—F2 | 1.286 (7) |
N1—C1 | 1.332 (5) | C7—F3 | 1.316 (6) |
N1—C2 | 1.366 (5) | C7—F1 | 1.334 (7) |
N2—C1 | 1.337 (5) | C8—F4 | 1.312 (6) |
N2—C3 | 1.363 (5) | C8—F6 | 1.315 (6) |
C1—C4 | 1.465 (5) | C8—F5 | 1.320 (6) |
C2—C3 | 1.324 (6) | ||
O3—S1—O4 | 118.7 (3) | C1—C4—H4A | 109.5 |
O3—S1—N3 | 117.5 (2) | C1—C4—H4B | 109.5 |
O4—S1—N3 | 106.7 (2) | H4A—C4—H4B | 109.5 |
O3—S1—C7 | 104.9 (2) | C1—C4—H4C | 109.5 |
O4—S1—C7 | 102.9 (3) | H4A—C4—H4C | 109.5 |
N3—S1—C7 | 103.9 (2) | H4B—C4—H4C | 109.5 |
O5—S2—O6 | 118.7 (3) | O1—C5—H5A | 109.5 |
O5—S2—N3 | 117.3 (2) | O1—C5—H5B | 109.5 |
O6—S2—N3 | 106.9 (2) | H5A—C5—H5B | 109.5 |
O5—S2—C8 | 104.8 (2) | O1—C5—H5C | 109.5 |
O6—S2—C8 | 103.6 (2) | H5A—C5—H5C | 109.5 |
N3—S2—C8 | 103.7 (2) | H5B—C5—H5C | 109.5 |
N1—O1—C5 | 110.5 (3) | O2—C6—H6A | 109.5 |
N2—O2—C6 | 110.3 (3) | O2—C6—H6B | 109.5 |
C1—N1—C2 | 111.7 (3) | H6A—C6—H6B | 109.5 |
C1—N1—O1 | 122.6 (3) | O2—C6—H6C | 109.5 |
C2—N1—O1 | 125.6 (3) | H6A—C6—H6C | 109.5 |
C1—N2—C3 | 112.0 (3) | H6B—C6—H6C | 109.5 |
C1—N2—O2 | 122.1 (3) | F2—C7—F3 | 110.6 (6) |
C3—N2—O2 | 125.8 (4) | F2—C7—F1 | 107.5 (5) |
S1—N3—S2 | 123.39 (19) | F3—C7—F1 | 106.8 (5) |
N1—C1—N2 | 103.4 (3) | F2—C7—S1 | 111.3 (4) |
N1—C1—C4 | 127.5 (4) | F3—C7—S1 | 112.1 (4) |
N2—C1—C4 | 129.1 (4) | F1—C7—S1 | 108.3 (4) |
C3—C2—N1 | 106.7 (4) | F4—C8—F6 | 107.9 (4) |
C3—C2—H2 | 126.6 | F4—C8—F5 | 109.1 (5) |
N1—C2—H2 | 126.6 | F6—C8—F5 | 108.3 (4) |
C2—C3—N2 | 106.1 (4) | F4—C8—S2 | 109.7 (3) |
C2—C3—H3 | 126.9 | F6—C8—S2 | 111.1 (3) |
N2—C3—H3 | 126.9 | F5—C8—S2 | 110.8 (3) |
C5—O1—N1—C1 | 106.1 (4) | C1—N2—C3—C2 | −1.0 (5) |
C5—O1—N1—C2 | −77.2 (5) | O2—N2—C3—C2 | −178.3 (3) |
C6—O2—N2—C1 | 103.0 (5) | O3—S1—C7—F2 | −56.0 (5) |
C6—O2—N2—C3 | −80.0 (5) | O4—S1—C7—F2 | 179.1 (5) |
O3—S1—N3—S2 | 21.3 (4) | N3—S1—C7—F2 | 68.0 (5) |
O4—S1—N3—S2 | 157.7 (3) | O3—S1—C7—F3 | 179.5 (4) |
C7—S1—N3—S2 | −94.0 (3) | O4—S1—C7—F3 | 54.6 (5) |
O5—S2—N3—S1 | 19.4 (4) | N3—S1—C7—F3 | −56.5 (5) |
O6—S2—N3—S1 | 155.5 (3) | O3—S1—C7—F1 | 61.9 (5) |
C8—S2—N3—S1 | −95.4 (3) | O4—S1—C7—F1 | −62.9 (4) |
C2—N1—C1—N2 | −0.4 (4) | N3—S1—C7—F1 | −174.1 (4) |
O1—N1—C1—N2 | 176.7 (3) | O5—S2—C8—F4 | 59.0 (4) |
C2—N1—C1—C4 | 177.5 (4) | O6—S2—C8—F4 | −66.1 (4) |
O1—N1—C1—C4 | −5.4 (6) | N3—S2—C8—F4 | −177.5 (3) |
C3—N2—C1—N1 | 0.8 (4) | O5—S2—C8—F6 | 178.2 (4) |
O2—N2—C1—N1 | 178.2 (3) | O6—S2—C8—F6 | 53.1 (4) |
C3—N2—C1—C4 | −177.0 (4) | N3—S2—C8—F6 | −58.4 (4) |
O2—N2—C1—C4 | 0.4 (6) | O5—S2—C8—F5 | −61.5 (4) |
C1—N1—C2—C3 | −0.2 (5) | O6—S2—C8—F5 | 173.5 (4) |
O1—N1—C2—C3 | −177.1 (3) | N3—S2—C8—F5 | 62.0 (4) |
N1—C2—C3—N2 | 0.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O4i | 0.95 | 2.40 | 3.253 (6) | 150 |
C2—H2···O6ii | 0.95 | 2.27 | 3.155 (5) | 156 |
C5—H5A···O5iii | 0.98 | 2.44 | 3.276 (5) | 143 |
Symmetry codes: (i) x, −y, z−1/2; (ii) x+1/2, y−1/2, z; (iii) x+1/2, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O4i | 0.95 | 2.396 | 3.253 (6) | 150 |
C2—H2···O6ii | 0.95 | 2.266 | 3.155 (5) | 156 |
C5—H5A···O5iii | 0.98 | 2.437 | 3.276 (5) | 143 |
Symmetry codes: (i) x, −y, z−1/2; (ii) x+1/2, y−1/2, z; (iii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H11N2O2+·C2F6NO4S2− |
Mr | 423.32 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 183 |
a, b, c (Å) | 12.4858 (6), 14.0212 (6), 9.8480 (4) |
β (°) | 98.179 (1) |
V (Å3) | 1706.51 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.18 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker D8 QUEST PHOTON 100 |
Absorption correction | Multi-scan (SADABS; Bruker, 2012) |
Tmin, Tmax | 0.851, 0.914 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24313, 3088, 3020 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.092, 1.05 |
No. of reflections | 3088 |
No. of parameters | 228 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.23 |
Absolute structure | Flack x determined using 1476 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.493 (15) |
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), ORTEP-3 for Windows (Farrugia, 2012), Mercury (Macrae et al., 2006).
Acknowledgements
Technical assistance by Michael Hilgärtner is acknowledged.
References
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The molecular structure of the title compound is shown in Fig. 1. The ions which build this salt, both 1,3-dialkyloxyimidazolium cations (Laus et al., 2010) and the bis(triflimide) anion (Bentivoglio et al., 2009; Laus et al., 2011), are known to exist as syn/anti conformers in the solid state. Thus, the methoxy substituents of the cation adopt an anti conformation with a C5—O1···O2—C6 torsion angle of 170.6 (4)°. The bis(triflimide) anion also assumes an anti conformation with a C7—S1···S2—C8 dihedral angle of 174.9 (2)°. Each cation donates three C—H···O═S hydrogen bonds to three anions (Fig. 2). The hydrogen bond parameters are summarized in Table 1. An intriguing intermolecular interaction between O3 of the anion and the π system of the imidazolium ring is observed. The pertinent O3···Cg distance is 2.971 Å, where Cg is the centroid of the heterocyclic ring. This interaction is directional with a S1═O3···Cg angle of 152°, and the crystal packing is shown in Fig. 3.
The cation in the structure of the related 1,3-dimethoxy-2-methylimidazolium tris(pentafluoroethyl)trifluorophosphate displayed the syn geometry (Laus et al., 2007). Anion···π interactions have been observed in related imidazolium salts (Froschauer et al., 2012).